EP1054040B1 - Azofarbstoffe, Verfahren zu deren Herstellung und deren Verwendung zum Färben oder Bedrucken von natürlichen oder synthetischen Materialien - Google Patents
Azofarbstoffe, Verfahren zu deren Herstellung und deren Verwendung zum Färben oder Bedrucken von natürlichen oder synthetischen Materialien Download PDFInfo
- Publication number
- EP1054040B1 EP1054040B1 EP20000810381 EP00810381A EP1054040B1 EP 1054040 B1 EP1054040 B1 EP 1054040B1 EP 20000810381 EP20000810381 EP 20000810381 EP 00810381 A EP00810381 A EP 00810381A EP 1054040 B1 EP1054040 B1 EP 1054040B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- dye
- alkyl
- dyeing
- dyes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 0 CCC(C)(CC(C)(C)C)c(cc1N=Nc2cc(S(O)(=O)=O)c(*)cc2)ccc1O Chemical compound CCC(C)(CC(C)(C)C)c(cc1N=Nc2cc(S(O)(=O)=O)c(*)cc2)ccc1O 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0014—Monoazo dyes prepared by diazotising and coupling from diazotized aminonaphthalene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
- C09B29/12—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the benzene series
Definitions
- the present invention relates to azo dyes and their use for dyeing or Printing nitrogen-containing or hydroxy-containing natural or synthetic Materials, especially synthetic polyamide fiber materials.
- the object underlying the present invention was to yellow or orange
- R 1 as C 1 -C 8 alkyl is, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl.
- R 2 as C 1 -C 8 alkyl is, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl.
- R 3 as C 1 -C 8 alkyl is, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl.
- R 4 as C 1 -C 8 alkyl is, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl.
- R 2 as C 1 -C 8 alkoxy is, for example, methoxy, ethoxy, propoxy and butoxy.
- -NH-CO-C 1 -C 4 -alkyl is preferably -NH-CO-CH 3 and -NH-CO-C 2 H 5 .
- Preferred as X is -CO-.
- R 1 is tert-butyl and methyl.
- R 2 is -C (CH 3 ) 2 CH 2 CH 3 , -C (CH 3 ) 2 CH 2 C (CH 3 ) 3 and tert-butyl R 3 is preferably ethyl and methyl.
- R 4 is methyl and hydrogen.
- R 1 is halogen, especially chlorine.
- R 2 is methoxy and halogen, especially chlorine.
- Methyl is particularly preferred as R 1 .
- Particularly preferred as R 2 is tert-butyl.
- Methyl is particularly preferred as R 3 .
- Hydrogen is particularly preferred as R 4 .
- the radical R 1 is preferably bonded in the ortho position to the hydroxy.
- the radical R 2 is preferably bonded in the para position to the hydroxy.
- the azo bridge is preferably bound in the ortho position to the hydroxy.
- the radical -NH-XR 3 is preferably bonded in the para position to the azo bridge.
- n is preferably the number 1.
- dyes of the formula (1) dyes of the formula are preferred used where R 1 , R 2 , R 3 , R 4 and X have the meanings and preferences given for the time being under the formula (1).
- Dyes of the formula (3) are particularly preferably used. These dyes are new.
- Another object of the invention are dyes of the formula represents what R 5 is hydrogen, methyl, tert. Butyl or chlorine, R 6 is methyl, tert-butyl, -C (CH 3 ) 2 CH 2 CH 3 , -C (CH 3 ) 2 CH 2 C (CH 3 ) 3 , methoxy, chlorine or phenyl, R 7 is methyl, and X -CO- are.
- dyes of the formula (1) are very particularly preferred and
- the dye of formula (111) is special important.
- the dyes of the formulas (1), (2) and (3) can be used as free acid or, preferably, in the form of salts, for example as Li, Na, K, NH 4 , triethanolamine or triisopropanolamine salts, or as Salts with a cation which is obtained by reacting triethanolamine with ethylene oxide and / or propylene oxide, be used.
- salts for example as Li, Na, K, NH 4 , triethanolamine or triisopropanolamine salts, or as Salts with a cation which is obtained by reacting triethanolamine with ethylene oxide and / or propylene oxide, be used.
- the dyes of the formulas (1) and (2) can be obtained, for example, by using a compound of the formula or the formula wherein R 3 , R 4 and X have the meanings given under the formula (1), diazotized in an acidic pH range and then with a compound of the formula wherein R 1 and R 2 have the meanings given under the formula (1), and an aqueous sodium hydroxide solution at a pH between 8 and 12, advantageously between 9.5 and 10.5.
- the compounds of the formulas (50) to (52) are known or can be prepared according to generally known ones Methods are made.
- the present invention furthermore relates to concentrated aqueous solutions of dyes, characterized in that they contain 5 to 50% by weight, in particular 10 to 50% by weight and preferably 20 to 50% by weight, based on the total weight of the solution. of a dye of formula (1).
- the dyes can be present in these concentrated aqueous solutions either as the free acid or as the salts described above.
- the concentrated aqueous solutions according to the invention can contain further additives, such as e.g. Urea, caprolactam or polyethylene glycol. Furthermore, the inventive concentrated aqueous solutions still fungal and / or bacterial growth contain inhibitory substances.
- the dye solutions according to the invention also have good hard water resistance and they can be diluted with water in any ratio, for example with the Production of the dye liquor without the dissolved dyes failing.
- the dyes of the formula (1) according to the invention can be used in the customary dyeing or Printing processes are applied.
- the dyeing liquors or printing pastes can also Water and the dyes further additives, for example wetting agents, anti-foaming agents, Leveling agents or agents influencing the property of the textile material, e.g. Plasticizers, Additives for flame retardant or dirt, water and oil repellent Agents and water softening agents and natural or synthetic thickeners, such as e.g. Alginates and cellulose ethers.
- the dyes of the formula (1) according to the invention are also for dyeing from short liquors, such as. for continuous dyeing processes or discontinuous and continuous foam coloring processes, suitable.
- the dyes of the formula (1) according to the invention are particularly good Mounting behavior, good solubility and printing paste stability as well as good combinability out. Furthermore, the dye solutions according to the invention have good storage stability on, e.g. their concentrated solutions at a temperature of -5 to + 40 ° C are stable for several months.
- the dyes of the formula (1) according to the invention are particularly suitable for dyeing or printing hydroxyl-containing or nitrogen-containing fiber materials. They are particularly suitable for dyeing or printing synthetic polyamide materials, such as polyamide 6 or polyamide 6.6, or silk, and are also suitable for dyeing or printing mixed fabrics or yarns made of wool and synthetic polyamide.
- the material mentioned, in particular textile material can be in a wide variety of processing forms, such as fiber, yarn, woven or knitted fabric and in particular in the form of carpets.
- the suspension obtained is metered in over the course of 30 minutes, at a temperature of 20-25 ° C., of a solution consisting of 3 parts of 4-tert-butylphenol, 10 parts of an aqueous 2N sodium hydroxide solution and 150 parts of water.
- the pH is kept at a value of 10 by adding an aqueous 2 normal sodium hydroxide solution.
- the resulting yellow suspension is stirred for 2 hours at a temperature of 20-25 ° C and a pH of 10 and filtered off.
- the product is washed with 100 parts of water and dried in vacuo at 70 ° C. 7.1 parts of a compound of the formula are obtained
- a leveling aid (based on the condensation product of a higher aliphatic amine and ethylene oxide) is added to 2000 parts by weight of demineralized water at room temperature. The bath is then adjusted to a pH of 6 using 4 parts by weight of sodium dihydrogen phosphate and 0.6 part by weight of disodium hydrogen phosphate.
- the resulting dye solution is mixed with 100 parts of polyamide-6.6 fiber material (Helancatrikot) and heats the dyebath to a temperature within 45 minutes of approx. 96 ° C. The temperature is kept for 45 to 60 minutes, then cooled to one Temperature of 70 ° C and removes the dyed material, which is rinsed with water and then is dried. A fabric dyed in a beige-brown shade is obtained.
- a leveling aid (based on the condensation product of a higher aliphatic amine and ethylene oxide) is added to 2000 parts by weight of demineralized water at room temperature.
- the bath is then adjusted to a pH of 6 using 4 parts by weight of sodium dihydrogen phosphate and 0.6 part by weight of disodium hydrogen phosphate.
- the dye solution obtained is mixed with 100 parts of polyamide-6.6 fiber material (Helancatrikot) and the dye bath is heated to a temperature of approx. 96 ° C. within 45 minutes. The temperature is maintained for 45 to 60 minutes, then cooled to a temperature of 70 ° C. and the material to be dyed is removed, which is rinsed with water and then dried.
- a fabric dyed in a lemon-yellow shade is obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
R2 als C1-C8-Alkyl ist z.B. Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, Pentyl, Hexyl, Heptyl und Octyl.
R3 als C1-C8-Alkyl ist z.B. Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, Pentyl, Hexyl, Heptyl und Octyl.
R4 als C1-C8-Alkyl ist z.B. Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, Pentyl, Hexyl, Heptyl und Octyl.
Bevorzugt als R1 ist tert.-Butyl und Methyl.
Bevorzugt als R2 ist -C(CH3)2CH2CH3, -C(CH3)2CH2C(CH3)3 und tert.-Butyl
Bevorzugt als R3 ist Ethyl und Methyl.
Bevorzugt als R4 ist Methyl und Wasserstoff.
Ebenfalls bevorzugt als R1 ist Halogen, insbesondere Chlor.
Ebenfalls bevorzugt als R2 ist Methoxy und Halogen, insbesondere Chlor.
Besonders bevorzugt als R2 ist tert.-Butyl.
Besonders bevorzugt als R3 ist Methyl.
Besonders bevorzugt als R4 ist Wasserstoff.
Der Rest R2 ist vorzugsweise in para-Position zum Hydroxy gebunden.
Die Azobrücke ist vorzugsweise in ortho-Position zum Hydroxy gebunden.
Der Rest -NH-X-R3 ist vorzugsweise in para-Position zu der Azobrücke gebunden.
R1, R2, R3, R4 und X die vorderhand unter der Formel (1) angegebenen Bedeutungen und Bevorzugungen haben.
R5 Wasserstoff, Methyl, tert. Butyl oder Chlor,
R6 Methyl, tert.-Butyl, -C(CH3)2CH2CH3, -C(CH3)2CH2C(CH3)3, Methoxy, Chlor oder Phenyl,
R7 Methyl, und
X -CO-
sind.
verwendet werden.
R3, R4 und X die unter der Formel (1) angegebenen Bedeutungen haben, in saurem pH-Bereich diazotiert und anschliessend mit einer Verbindung der Formel worin
R1 und R2 die unter der Formel (1) angegebenen Bedeutungen haben,
und einer wässrigen Natriumhydroxidlösung bei einem pH-Wert zwischen 8 und 12, vorteilhafterweise zwischen 9,5 und 10,5 umsetzt.
Die Farbstoffe können in diesen konzentrierten wässrigen Lösungen entweder als freie Säure oder als die vorderhand beschriebenen Salze vorliegen.
Das genannte Material, insbesondere Textilmaterial, kann dabei in den verschiedensten Verarbeitungsformen vorliegen, wie z.B. als Faser, Garn, Gewebe oder Gewirke und insbesondere in Form von Teppichen.
Die erhaltene Suspension wird innerhalb von 30 Minuten, bei einer Temperatur von 20-25°C, einer Lösung bestehend aus 3 Teilen 4-tert.-Butylphenol, 10 Teilen einer wässrigen 2N Natriumhydroxid-Lösung und 150 Teilen Wasser zudosiert. Während des Zudosierens wird der pH durch Zugabe einer wässrigen, 2 normalen Natriumhydroxid-Lösung bei einem Wert von 10 gehalten. Die entstandene gelbe Suspension wird 2 Stunden bei einer Temperatur von 20-25°C und einem pH-Wert von 10 nachgerührt und abfiltriert. Das Produkt wird mit 100 Teilen Wasser gewaschen und im Vacuum bei 70°C getrocknet. Man erhält 7.1 Teile einer Verbindung der Formel
0,10 Gewichtsteile des Farbstoffes gemäss Beispiel 12, der in Form der freien Säure der Verbindung der Formel entspricht,
0,06 Teile eines Farbstoffes der in Form der freien Säure der Verbindung der Formel entspricht,
0,02 Teile eines Farbstoffes der in Form der freien Säure der Verbindung der Formel entspricht,
0,04 Teile eines Farbstoffes der in Form der freien Säure der Verbindung der Formel entspricht,
0,03 Teile eines Farbstoffes der in Form der freien Säure der Verbindung der Formel entspricht, und
0,13 Teile eines Farbstoffes der in Form der freien Säure der Verbindung der Formel entspricht, zu.
In die erhaltene Farbstofflösung geht man mit 100 Teilen Polyamid-6,6 Fasermaterial (Helancatrikot) ein und erwärmt das Färbebad innerhalb von 45 Minuten auf eine Tempereatur von ca. 96°C. Man hält die Temperatur 45 bis 60 Minuten, kühlt anschliessend auf eine Temperatur von 70°C ab und entnimmt das Färbegut, welches mit Wasser gespült und anschliessend getrocknet wird. Man erhält ein in einem zitronengelben Farbton gefärbtes Gewebe.
Claims (9)
- Verfahren zur Herstellung der Farbstoffe der Formel (3) gemäss Anspruch 1, dadurch gekennzeichnet, dass man eine Verbindung der Formel worin
R7 und X die unter der Formel (3) angegebenen Bedeutungen haben, in saurem pH-Bereich nitriert und anschliessend mit einer Verbindung der Formel worin
R1 und R2 die unter der Formel (3) angegebenen Bedeutungen haben,
und einer wässrigen Natriumhydroxidlösung bei einem pH-Wert zwischen 8 und 12, vorteilhafterweise zwischen 9,5 und 10,5 umsetzt. - Konzentrierte wässrige Lösungen von Farbstoffen, dadurch gekennzeichnet, dass sie 5 bis 50 Gew.-%, bezogen auf das Gesamtgewicht der Lösung, eines Farbstoffes der Formel (3) gemäss Anspruch 1 enthalten.
- Konzentrierte wässrige Lösungen von Farbstoffen, dadurch gekennzeichnet, dass sie 5 bis 50 Gew.-%, bezogen auf das Gesamtgewicht der Lösung, eines Farbstoffes der Formel (111) gemäss Anspruch 2 enthalten.
- Verfahren zum Färben oder Bedrucken von hydroxylgruppenhaitigen oder stickstoffhaltigen Fasermaterialien, dadurch gekennzeichnet, dass man einen oder mehrere Farbstoffe der Formel (1) verwendet, worin
R1 Wasserstoff, Halogen, C1-C8-Alkyl, -NH-CO-C1-C4-Alkyl oder Phenyl,
R2 Wasserstoff, Halogen, C1-C8-Alkyl, C1-C8-Alkoxy, -NH-CO-C1-C4-Alkyl oder Phenyl,
R3 Wasserstoff, C1-C8-Alkyl oder Phenyl,
R4 Wasserstoff, Halogen oder C1-C8-Alkyl, und
X -CO-, -COO- oder -SO2- sind, und
n eine Zahl 1 oder 2 ist. - Verwendung der Farbstoffe der Formel (1) gemäss Anspruch 6 zum Färben oder Bedrucken von hydroxylgruppenhaltigen oder stickstoffhaltigen Fasermaterialien.
- Verwendung gemäss Anspruch 7 zum Färben oder Bedrucken von synthetischen Polyamidfasermaterialien.
- Die mit den Farbstoffen gemäss Anspruch 6 gefärbten oder bedruckten hydroxylgruppenhaltigen oder stickstoffhaltigen Fasermaterialien.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20000810381 EP1054040B1 (de) | 1999-05-10 | 2000-05-04 | Azofarbstoffe, Verfahren zu deren Herstellung und deren Verwendung zum Färben oder Bedrucken von natürlichen oder synthetischen Materialien |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99810414 | 1999-05-10 | ||
EP99810414 | 1999-05-10 | ||
EP20000810381 EP1054040B1 (de) | 1999-05-10 | 2000-05-04 | Azofarbstoffe, Verfahren zu deren Herstellung und deren Verwendung zum Färben oder Bedrucken von natürlichen oder synthetischen Materialien |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1054040A1 EP1054040A1 (de) | 2000-11-22 |
EP1054040B1 true EP1054040B1 (de) | 2003-01-08 |
Family
ID=26073867
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20000810381 Expired - Lifetime EP1054040B1 (de) | 1999-05-10 | 2000-05-04 | Azofarbstoffe, Verfahren zu deren Herstellung und deren Verwendung zum Färben oder Bedrucken von natürlichen oder synthetischen Materialien |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP1054040B1 (de) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH559231A5 (de) * | 1971-01-28 | 1975-02-28 | Sandoz Ag | |
GB1556622A (en) * | 1975-08-08 | 1979-11-28 | Ici Ltd | Method of improving the water-solubility of acid dyes |
-
2000
- 2000-05-04 EP EP20000810381 patent/EP1054040B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP1054040A1 (de) | 2000-11-22 |
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